Slide 1

Refractory Oxides with Tunable Porosity and Geometry as Versatile Fast-Release

Solid Catchers for Rare Isotopes

Sponsor: Office of Nuclear Physics, DOE Program Officer: Dr. Manouchehr Farkhondeh

Phase II Contract Number: DE-SC0007572

Small Business InnoSense LLC

2531 West 237th Street, Suite 127 Torrance, CA 90505

Collaborator Dr. Jerry Nolen Physics Division

Argonne National Laboratory

Principal Investigator Uma Sampathkumaran (310) 530-2011 x 103

uma.sampathkumaran@innosense.us

Nuclear Physics SBIR/STTR Exchange Meeting August 6-7, 2015

Slide 2

About InnoSense LLC Motivation Relevance to Nuclear Physics Programs Phase II Accomplishments

Fabrication of Refractory Porous Oxides Off-Line Extended Heating Evaluations Simulations In Beam Evaluations

Summary Commercialization Status Acknowledgments

Presentation Overview

Slide 3

About InnoSense LLC

■ Established in 2002 by private investment, R&D operations in 2004, housed in a recently expanded 9,000 square feet laboratory facility located in Torrance, California.

■ Key laboratories include five “wet” chemical facilities equipped with fume hoods, a clean room, a spectroscopy facility, optics and testing laboratory, and two machine shops.

■ 18 employees, including 4 PhD, 3 MS and 3 MBA degree holders.

Slide 4

InnoSense LLC – Core Technologies

Slide 5

Refractory Hot Catchers for Rare Isotopes

Primary purpose of porous oxide monolith is to catch 9C−22C isotopes and convert them to 9C16O− 22C16O expected to be released almost as a noble gas.

Slide 6

Catcher Materials Under Investigation

Refractory Catcher Beam Expected Isotope

Tungsten-coated SiO2 Aerogel 18O (typical) 8-11Li 6,8He

Carbon Aerogel 16O, 48Ca, etc. 12C14O–12C24O 12C14O2–12C24O2

Yttria-Stabilized Zirconia and Hafnia Porous Monolith

12C, 48Ca, etc. 9C16O–22C16O 9C16O2–22C16O2

Sintering-inhibited Tungsten, Tungsten + Hafnia Tungsten Carbide

4He, 7Li 4He, 7Li, 13C,120Sn 18O

8-11Li 6,8He,120Sn,120SnS 12C18O, 12C18O2

Slide 7

Catcher Thickness Considerations

Desired area density (η ) for efficient isotope capture is ~ 3 g/cm2 or more

Area density can be related to the volumetric apparent density (ρ) measured by: η =ρL

Meter(s) long gas catcher is replaced by a relatively small (cm-long) catcher

Catcher

Slide 8

Background on ISOL Target Materials

Isotope Separation On-Line (ISOL) used to generate radionuclides Targets are used with high power beams Isotopes are produced by reactions of the beam with

target material Target must be dense enough to stop energetic

beam, yet porous enough to allow rapid diffusion of radionuclides to the accelerator source Must be thermally conductive to withstand beam

power Targets are heated to > 2000 °C to increase diffusion

rates of radioactive nuclides

Slide 9

Benefits When Used in Catcher Mode

■ Catchers used to stop high energy radioactive isotopes created in a separate production target up stream

■ In the catcher mode, thermal conductivity is less relevant since the beam power is deposited in the thermally separated production target irradiated with heavy ion beams

■ No radiation damage when used in catcher mode since only secondary radioisotope beams impinge on it

■ Selection of materials is open to new approaches that cannot work with ISOL targets, e.g. aerogels with low thermal conductivity

■ The porous refractory materials will theoretically offer more stopping power and fast-release for the generation of intense rare isotopes

■ The refractory nature potentially allows them to be used as: ■ Compact isotope catcher/ion source placed in the first focal plane of

the fragment separator with the capability of selective harvesting for isotopes for different applications

Slide 10

Technical Objectives and Milestones Accomplished

Objective 1. Refine formulations and processing conditions to reproducibly fabricate porous, solid catchers of yttria-stabilized zirconia and hafnia.

Milestone 1: Exceeded targets by achieving open porosities ranging from 50–75% after 30 minutes at 1500 °C compared to the 800 °C planned for (Month 9 of Year 1)

Objective 2. Evaluate porous monoliths off-line in long duration heating at temperatures ranging from 1000−1500 °C.

Milestone 2: Achieved higher open porosities of 41–51% (targeted 30–50%) after long-term heating at 1500 °C, simulating a production run (Month 4 of Year 2).

Objective 3. Develop a new method for in-beam evaluation of solid catchers for rare isotopes using accelerated stable beams and a very sensitive residual gas analyzer (RGA).

Milestone 3: The first demonstration of CO release was accomplished using the off-line RGA apparatus commissioned at Argonne (Month 4 of Year 2).

Objective 4: Evaluate candidate porous oxide (YSZ and HfO2) monoliths with in-beam studies using new apparatus.

Milestone 4: The first predictions of the preliminary simulations on oxide systems were completed and verified by experimental observations of CO release at temperatures below 1000 °C (Month 6 of Year 2).

Milestone 5: The RGA apparatus was moved to FSU and used for the first on-line validation of its sensitivity by measuring the release of 4He atoms implanted in an alumina nanopowder sample (Month 12 of Year 2.

Slide 11

Tape Casting Process to Fabricate Porous Oxides

Pressed Green Disk

Carver Hydraulic Press

Dry Cast Tape

½” Die Punch

Ball Mill Die

Die in Press

Slide 12

Tape Cast Porous Oxide Monoliths

Diced Stacked Hot Pressed Tape Disks After 1500 °C firing

Dye Penetrant Test

Top Bottom

Originally white disk turns red upon wetting by dye

Slide 13

Grain Growth Inhibition Demonstrated

Imaged at x1k and x50k

HfO2 after 24 h@1500 °C HfO2 + carbon wires HfO2 + carbon wires + GGI

Needle like pores Grain boundary phase

Slide 14

Fracture Surfaces of Hafnia Formulations

Slide 15

Fracture Surfaces of YSZ Formulations

Slide 16

Thermo-Chemical Simulation Using the HSC Program for CO Release from Al2O3 + Trace C

Significant conversion of elemental C to volatile CO molecule at 700 °C. Al2O3 breaks down at <800 °C – Not a practical catcher material when higher

temperatures are used to enhance diffusion rates from solid catcher.

Slide 17

Simulation of CO Release from Y2O3 + Trace C

Y2O3 + trace C mixture indicating significant conversion of elemental C to the volatile CO molecule at 800 °C.

Slide 18

Simulation of CO Release from Hafnia + Trace C

HfO2+ trace C mixture indicating significant conversion of elemental C to the volatile CO molecule over a wide range from ~750 °C to ~1700 °C.

Slide 19

RGA Installed in the FSU Tandem Accelerator

Beam comes from the right, the RGA is on the left, and the sample chamber is in the center below the turbo pump.

Close-up of the sample chamber with the sample holder visible through the window. Beam enters from the left. A beam diagnostics cross is upstream of the sample chamber.

Slide 20

Sample Holder and Heater in RGA

Left and left-center: Alumina crucible, tungsten heater, and current feed-throughs. Right-center: View through the chamber window of the sample holder and its heat shield. Right: View of the sample with the heater on.

Slide 21

RGA Spectra of 4He from Calibrated Leak and from Alumina Stopper Implanted with 4He

RGA spectra between masses 3 and 12. Left– After 4He implantation with sample at room temperature; Left-center− Same region after heating to ~1000 °C in 30 s showing release of He gas; Right-center– Same

region 40 s later showing He depletion from sample; Right– Same region with cold and calibrated He leak open to chamber (leak rate is 6E10 atoms/s equivalent to 10 particle nanoamps of beam current.

Slide 22

Summary

YSZ porous solid catchers 1–2 mm thick • Density ranging from 2.74–3.04g/cm3

• Intrusion or open porosity ranged from 42–47% Hafnia porous solid catchers 1–2 mm thick

• Density ranging from 3.93–4.28 g/cm3 • Intrusion or open porosity ranged from 47–51%.

Grain growth inhibition is demonstrated with porogens, calcium oxide and cerium oxide. New RGA method for release characteristics of stable isotopes

developed and demonstrated mass 29 (13CO release) New heater design completed for in-beam studies Beam line tests demonstrated molecular 13CO release from

nanoalumina powder with trace C additive and calibrated 4He leak First beamline studies of hafnia monoliths demonstrated trace

13CO release. More runs planned at FSU in a dedicated beam line starting in September 2015.

Slide 23

Army: W15QKN-09-C-0153 Passive Temperature Dosimeter

Commercialization Status

Phase IIE Funding Correlation Testing at Yuma

Proving grounds Sep 2015. Anticipate production of

~ 44,000 units in March 2016 for one type of ammunition

PC lens and PU visor

Army: W911NF-11-C-0056 Permanent anti-fog coating

DOD RIF award from DTRA - 2015 Partnered with eyewear safety products

manufacturer for scale up and marketing Automotive headlamps – Evaluations

PO for silica aerogel coatings on metal lattices - Invoiced 7/4/15

Prior DOE ONP funding enabled us to develop the technology for monoliths and build capabilities

Slide 24

DOE and the Office of Nuclear Physics to support

these efforts through the following grants DE-SC0007572 and DE-SC0011346

Program Officer – Dr. Manouchehr Farkhondeh

Dr. Georg Bollen for technical discussions and sustained interest to evaluate the catcher materials at FRIB

Dr. Dan Stracener for the ThermoCalc simulations of release studies

Dr. Elizabeth Bartosz - suggestion to approach FSU for beam time.

Dr. Ingo Weidenhover at FSU for beam-line studies at the FN Tandem accelerator

Acknowledgments